U.S. patent number 3,867,404 [Application Number 05/323,685] was granted by the patent office on 1975-02-18 for new isoindolinone pigments and process for their manufacture.
This patent grant is currently assigned to Ciba-Geigy Corporation. Invention is credited to Ernst Model, Andre Pugin, Jost von der Crone.
United States Patent |
3,867,404 |
von der Crone , et
al. |
February 18, 1975 |
New isoindolinone pigments and process for their manufacture
Abstract
Isoindolinones of the formula ##SPC1## Wherein Hal denotes a
chlorine or bromine atom, X denotes a direct bond or a carbocyclic
or heterocyclic aromatic radical, Y denotes an oxygen or sulphur
atom, R.sub.3 and R.sub.4 denote hydrogen lower alkyl or aryl
radicals and R denotes a hydrogen atom or a lower alkyl, lower
cycloalkyl, aralkyl or aryl group, Z denotes a hydrogen atom, n
denotes the number 0 to 3, m denotes the number 1 to 4, p denotes
the number 0 to 2 and q and r denote the numbers 0 or 1, with the
sum of n+m+p being at most 4 are valuable pigments for solering
plastics and lacquers in yellow to orange shades of outstanding
fastness properties.
Inventors: |
von der Crone; Jost (Riehen,
CH), Model; Ernst (Basle, CH), Pugin;
Andre (Riehen, CH) |
Assignee: |
Ciba-Geigy Corporation
(Ardsley, NY)
|
Family
ID: |
4191194 |
Appl.
No.: |
05/323,685 |
Filed: |
January 15, 1978 |
Foreign Application Priority Data
Current U.S.
Class: |
548/460; 534/738;
534/790; 534/797; 548/161; 548/180; 548/257; 548/261; 548/480 |
Current CPC
Class: |
C09B
26/02 (20130101); C09B 43/11 (20130101); C08K
5/0041 (20130101); C07D 209/50 (20130101); C09B
57/04 (20130101) |
Current International
Class: |
C07D
209/00 (20060101); C07D 209/50 (20060101); C08K
5/00 (20060101); C09B 26/02 (20060101); C09B
43/11 (20060101); C09B 26/00 (20060101); C09B
57/00 (20060101); C09B 43/00 (20060101); C09B
57/04 (20060101); C07d 027/50 () |
Field of
Search: |
;260/325,165,240,38B |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3758497 |
September 1973 |
Pugin et al. |
|
Primary Examiner: Narcavage; Joseph A.
Attorney, Agent or Firm: Cavalieri; Vincent J.
Claims
1. An isoindolinone pigment of the formula ##SPC16##
wherein Hal denotes chlorine or bromine, X denotes a direct bond, a
carbocyclic radical selected from the group consisting of
naphthylene, or a group having the formula ##SPC17##
wherein X.sub.1, V.sub.1 V.sub.2 and Z.sub.2 denote hydrogen,
halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon
atoms, X.sub.2 denotes sulphur, --NH--CO--, --NH--CO--NH--,
--CH=CH--or --N=N--, Z.sub.1 is halogen, alkyl of 1 to 4 carbon
atoms, alkoxy of 1 to 4 carbon atoms, phenylazo, phenylazo
substituted with methyl or acetylamino, or a heterocyclic aromatic
radical, selected from the group consisting of ##SPC18##
Y denotes oxygen or sulphur, R.sub.3 and R.sub.4 denote hydrogen,
lower alkyl or an aryl radical selected from the group consisting
of chlorophenyl, or dichlorophenyl, and R denotes hydrogen, lower
alkyl, lower cycloalkyl, benzyl or aryl selected from the group
consisting of phenyl, chlorophenyl, methylphenyl, dichlorophenyl,
dimethyl-phenyl, methoxyphenyl or naphthyl, Z denotes hydorgen, n
denotes the number 0 to 3, m denotes the number 1 to 4, p denotes
the number 0 to 2 and q and r
2. An isoindolinone pigment according to claim 1, of the formula
##SPC19##
wherein Y.sub.1 denotes chlorine or the --OR group and R and X have
the
3. An isoindolinone pigment according to claim 2, of the formula
##SPC20##
wherein X has the indicated meaning and R.sub.2 denotes alkyl
containing 1
4. An isoindolinone pigment according to claim 2, of the formula
##SPC21##
5. The isoindolinone pigment according to claim 1 wherein X denotes
the radical of the formula ##SPC22##
wherein X.sub.1 denotes hydrogen or halogen or alkyl containing
from 1 to 4 carbon atoms or alkoxy containing 1 to 4 carbon atoms
and Z.sub.1 denotes alkyl containing from 1 to 4 carbon atoms,
alkoxy containing 1 to 4 carbon
6. The compound according to claim 2 of the formula ##SPC23##
7. The compound according to claim 2 of the formula ##SPC24##
8. The compound according to claim 2 of the formula ##SPC25##
9. The compound according to claim 2 of the formula ##SPC26##
10. The compound according to claim 2 of the formula ##SPC27##
Description
It has been found that new valuable isoindolinone pigments of the
formula ##SPC2##
Wherein Hal denotes a chlorine or bromine atom, X denotes a direct
bond or a carbocyclic or heterocyclic aromatic radical, R.sub.3 and
R.sub.4 denote hydrogen atoms or alkyl or aryl radicals, Y denotes
an oxygen or sulphur atom, R denotes a hydrogen atom or an alkyl,
cycloalkyl or aryl group which is optionally substituted, for
example by alkoxy, aryloxy, cycloalkyl, aryl or heterocyclic
radicals, Z denotes a hydorgen atom, n denotes the number 0 to 3 m
denotes the number 1 to 4, , p denots the number 0 to 2 and r and q
denote 0 or 1, with the sum of the n+m+p+ being at most 4, are
obtained if a diamine of the formula ##SPC3##
Is condensed in the molar ratio of 1:2 with an isoindolinone of the
formula ##SPC4##
Wherein V denotes a group of the formula ##SPC5##
Wherein X.sub.2 denotes an imino or thio group and Y.sub.2 denotes
a halogen atom, a lower alkoxy group or a secondary amino
group.
The dyestuffs according to the invention preferably correspond to
the formulae ##SPC6##
Wherein Y.sub.1 denotes a chlorine atom or the --OR group, and
R.sub.2 and X have the indicated meaning, and especially of the
formula ##SPC7##
Wherein X has the indicated meaning and R.sub.2 denotes a lower
alkoxy group.
The isoindolinones to be used as starting substances contain, in
the 2-position, an imino or thio grup, 2 halogen atoms, 2 tertiary
amino groups, for example piperidino or morpholino groups, or
especially 2 lower alkoxy groups, preferably methoxy groups.
The isoindolinones preferably correspond to the formula
##SPC8##
And especially to the formula ##SPC9##
With R and Y.sub.1 in the indicated formulae having the indicated
meaning and R.sub.1 and R.sub.2 denoting lower alkoxy groups.
The 3,3-dialkoxy-isoindolinones are obtained according to a known
process by reaction of a o-cyanobenzoic acid alkyl ester of the
formula ##SPC10##
With an alkali alcoholate solution in a lower alcohol. As a rule it
is not necessary to isolate the isoindolinone thus obtained which
can, in most cases, be employed directly for the reaction with the
diamine.
The 3-imino-isoindolinones are obtained according to a known
process by reaction of an o-cyano-benzoic acid alkyl ester of the
formula IX with ammonia.
The o-cyanobenzoic acid alkyl esters are in turn obtained in
accordance with the process laid down in Patent application Ser.
No. 323,686, filed Jan. 15, 1973, by reaction of the ammonium salt
of a tetrahalogeno- or dihalogeno-o-cyanobenzoic acid with alkali
alcoholates, alkali phenolates or alkali mercaptides and
esterifciation of the reaction product with a dialkyl sulphate.
In the diamines of the formula Ia which also serve as starting
substances X denotes, in the simplest case, a direct bond. X can
als represent a carbocyclic or heterocyclic aromatic radical,
especially a divalent aromatic radical possessing at most two
benzene nuclei.
Where a bicyclic divalent aromatic radical is concerned, the two
benzene radicals can be bonded to one another by a direct bond or a
bridge. Possible bridges are, for example, sulphur or oxygen atoms,
imino groups and the atomic groupings of the formulae --NH--CO--,
--NH--CO--NH--, --CH=CH--and --N=N--.
As examples of bicyclic diamines of which the benzene radicals are
bonded directly to another there may be mentioned the
diaminodiphenyls, especially those of formula ##SPC11##
wherein Z.sub.2 denotes a hydrogen or halogen atom or an alkyl or
alkoxy group containing 1 to 4 carbon atoms.
Amongst the series of the diamines of which the benzene radicals
are bonded to one another via a bridge there may especially be
mentioned those of the formula ##SPC12##
wherein X.sub.1, V.sub.1, V.sub.2 and Z.sub.2 denote hydrogen or
halogen atoms, alkyl or alkoxy groups containing 1 to 4 carbon
atoms and X denotes a sulphur atom or a group of the formulae
--NH--CO--, --NH--CO--NH--, --CH=CH-- or --N=N--.
Diaminopyrenes, diaminofluorenes, diaminochrysenes,
diaminonaphthalenes, diaminopyrenes or diaminofluoranthenes may be
mentioned as further examples of polycyclic diamines.
Finally there may also be mentioned heterocyclic diamines such as
diaminopyridines, diaminophenylene oxides, diaminodiphenylene
sulphones, diaminocarbazoles, diaminobenzimidazoles,
diamino-bis-imidazoles, diamino-di-benzimidazolyls or
diamino-benzthiazoles.
Finally it is also possible to use, as diamines, dihydrazones of
dialdehydes or diketones of hydrazones of aminoaldehydes or
aminoketones.
The phenylenediamines are of particular interest, especially those
of the formula ##SPC13##
wherein X.sub.1 has the indicated meaning and Z.sub.1 denotes a
halogen atom, an alkyl or alkoxy group containing 1 to 4 carbon
atoms or a phenylazo group.
The following diamines may be mentioned as examples: hydrazine,
1,4-diaminobenzene, 1,3-diaminobenzene,
1,3-diamino-4-methylbenzene, 1,3-diamino-4-methoxybenzene,
1,3-diamino-2-methylbenzene, 1,3-diamino-2,5-dichlorobenzene,
1,4-diamino-2 chlorobenzene, 1,4-diamino-2-bromobenzene,
1,4-diamino-2,5 -dichlorobenzene, 1,4-diamino-2-methylbenzene,
1,4-diamino-2,5 -dimethylbenzene, 1,4-diamino-2-methoxybenzene,
1,4-diamino-2,5 -dimethoxybenzene,
1,4-diamino-2-chloro-5-methylbenzene,
1,4-diamino-2-chloro-5-methoxybenzene, 1,4-diamino-2-chloro-5
ethoxybenzene, 1,4-diamino-2,5-diethoxybenzene,
4,4'-diamino-diphenyl, 4,4'-diamino-3,3'-dichlorodiphenyl,
4,4'-diamino-3,3' -dimethyldiphenyl,
4,4'-diamino-3,3'-dimethoxydiphenyl, 4,4'
-diamino-3,3'-diethoxydiphenyl, 2,2'-diamino-diphenyl, 4,4'
-diamino-dephenylsulphide, 4,4'-diamino-benzoylaniline, 4,4'
-diamino-2-ethoxy-benzoylaniline,
3,3'-diamino-2,2'-dimethoxy-benzoylaniline,
4,4'-diamino-diphenylurea, 4,4'-diamino-
3,3'-dimethoxy-diphenylurea, 4,4'-diaminostilbene,
4,4'-diaminoazobenzene, 2-methyl-4,4'-diaminoazobenzene,
2-methoxy-4, 4'-diaminoazobenzene,
2,5-dimethyl-4,4'-diaminoazobenzene,
2,5,2'-trimethyl-4,4'-diaminoazobenzene,
3-methyl-2'-methoxy-4,4'-diaminoazbenzene,
3-chloro-2'-methyl-4,4'-diaminoazobenzene,
4-chloro-3,4'-diaminoazobenzene, 2 -chloro-4,3'-diaminoazobenzene,
2-methyl-4,3'-diaminoazobenzene, 2-methoxy-4,3'-diaminoazobenzene,
2,4-diaminoazobenzene, 5-methoxy-2,4-diaminoazobenzene,
2,4-diamino-3', 5'-dimethyl-4'-acetylaminoazobenzene,
2,4-diamino-5-methoxy-3',5'-dichloro-4'-acetylaminoazobenzene, 4,4'
-diamino-phenyl-1-azo-naphthalene-1' , 4,4'-diaminobenzophenone,
4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane,
2,2'-diaminodibenzyl, 1,4 -diaminonaphthalene,
1,5-diaminonaphthalene, 2,7-diaminofluorene,
4,11-diaminofluoranthene, 3,8-diaminopyrene, 2,8-diaminochrysene,
2,6-diaminopyridine, 2,6-diaminocarbazole, 3,6-diamino-diphenylene
oxide, 2,7-diaminodiphenylene oxide, 2,6-diaminodiphenylene oxide,
2,7-diaminodiphenylene sulphone, 2,6-diaminobenzthiazole,
2-(4'-aminophenyl)-6-amino-benzthiazole,
terephthalaldehyde-dihydrazone,
4,4'-diphenyl-dialdehyde-dihydrazone,
2,5-thiophenedialdehyde-di-hydrazone,
1,4-diacetylbenzene-dihydrazone, 4-aminobenzaldehyde-hydrazone,
4-aminoacetophenone-hydrazone, 4-aminobenzophenone-hydrazone,
4,-amino-4'methylbenzophenone-hydrazone, glyoxal-dihydrazone and
diacetyl-dihydrazone.
The condenstation in part already takes place in the cold, if
necessary on warming the intimately mixed components, and
particularly advantageously in the presence of inert organic
solvents, that is to say solvents which do not participate in the
reaction.
If starting from 3-imino-, 3-thio- or 3,3-bis-tert.
-amino-isoindolin-1-ones or from alkali metal salts of the
3,3'-dialkoxy-isoindolin-1-ones organic solvents which are miscible
with water are advantageously used, for example lower aliphatic
alcohols, such as lower alkanols, for example methanol, isopropanol
or butanol, lower cyclic ethers, such as dioxane, ethylene glycol
monomethyl ether and lower aliphatic ketones, such as acetone,
Here, the condensation already takes place at relatively low
temperatures. The reaction is advantageously carried out in the
presence of agents which bind bases; as examples of such agents
there may be mentioned lower fatty acids which can then
simultaneously serve as solvents, especially acetic acid.
When using 3,3-dihalogeno-isoindolin-1-ones organic solvents which
are free of hydroxyl groups are preferred, such as hydrocarbons,
for example aromatic hydrocarbons, such as benzene, toluene,
xylene, tetrahydronaphthalene or diphenyl, or cycloaliphatic
hydrocarbons, for example cyclohexane, but also halogenated
hydrocarbons, such as aliphatic halogenated hydrocarbons, for
example carbon tetrachloride or tetrachloroethylene, or aromatic
halogenated hydrocarbons, such as chlorobenzene or dichlorobenzenes
and trichlorobenzenes, also aromatic nitro-hydrocarbons, such as
nitrobenzene, ethers, namely aliphatic ethers, such as dibutyl
ether, aromatic ethers, such as diphenyl ether, or cyclic ethers,
such as dioxane, and also ketones, such as acetone, or esters,
especially esters of lower fatty acids with lower alkanols, such as
ethyl acetate, in the presence of acid-binding agents.
The new pigment precipitates from the reaction medium immediately
after it has formed. For certain purposes it can be used directly
as the crude pigment; however it is advantageous to condition it,
according to methods which are in themselves known, before it is
used, for example by extraction with organic solvents or by
grinding with grinding auxiliaries which can subsequently be
removed again, for example salts or especially hexachloroethane, or
by alkaline reprecipitation. In this way the purity, tinctorial
strength and transparency can be improved yet further.
The new dyestuffs are valuable pigments which in a finely divided
form can be used for pigmenting high molecular organic material,
for example cellulose ethers and cellulose esters, such as
ethylcellulose, acetyl-cellulose or nitrocellulose, polyamides,
polyurethanes or polyesters, natural resins or synthetic resins,
for example aminoplasts, especially thermoplastic and curable
acrylic resins, urea-formaldehyde and melamine-formaldehyde resins
and also alkyd resins, phenoplasts, polycarbonates, polyolefines,
such as polystyrene, polyvinyl chloride, polyethylene,
polypropylene, polyacrylonitrile, polyacrylic acid esters, rubber,
casein, silicone and silicone resins, individually or as mixtures.
Here it does not matter whether the high molecular compounds
mentioned are in the form of plastic masses or melts or in the form
of spinning solutions, lacquers, paints or printing inks. Depending
on the end use it proves advantageous to use the new pigments as
toners or in the form of preparations. The new pigments are
distinguished by high fastness, especially by outstanding fastness
to light, migration and weathering.
EXAMPLE 1
7.9 g of 3-imino-4,5,7-trichoro-6methylmercaptoisoindolin-1-one and
1.35 g. of p-phenylenediamine in 100 ml of glacial acetic acid are
heated to the reflux temperature for 1/2hour. The pigment formed is
filtered off hot and washed with methanol and water. After drying,
7.5 g of a yellowish-tinged orange pigment, which can be employed
for pigmenting lacquers and plastics, are obtained. The fastness to
migration and to light is outstanding.
EXAMPLE 2
If instead of the methylmercapto compound 10.2 g of
3-imino-4,5,7-trichloro-6-phenoxy-isoindolin-1-one are used, a
strongly coloured yellow pigment is obtained, which also shows very
good fastness to migration and to light.
EXAMPLE 3
18 g of 3,3,6-trimethoxy-4,5,7-trichloro-iso-indolin-1-one and 4.9
g of 3,6-diaminodiphenylene oxide in a mixture of 100 ml of glacial
acetic acid and 100 ml of o-dichlorobenzene are heated to the
reflux temperature for 1 hour. The insoluble dyestuff is filtered
off at 100.degree.C and washed with methanol, acetone and water.
After drying, 17 g of a pigment which is distinguished by a pure
medium yellow shade and is fast to migration in PVC and
outstandingly fast to light in lacquers are obtained.
Example 4
15.5 g of 3,4,6-trichloro-5-methoxy-o-cyanobenzoic acid methyl
ester are stirred with 70 ml of methanol and 8.8 g of a 30.6
percent strength solution of sodium methylate in methanol for 1/2
hour. The sodium salt of
3,3,6-trimethoxy-4,5,7-trichloroisoindolin-1-one is thereby
produced. 2,7 g of p-phenylenediamine are now added and the mixture
is subsequently stirred for 2 hours at room temperature and is then
diluted with 100 ml of o-dichlorobenzene. The reaction mixture is
heated to 100.degree.C whilst distilling off the methanol and
stirring well. After adding a further 100 ml of o-dichlorobenzene
and 10 ml of glacial acetic acid the temperature is raised to
140.degree.-150.degree.C and maintained for 2 hours. The insoluble
dyestuff is filtered off at 100.degree.C and washed with alcohol,
acetone and water. After drying, 15.6 g of a reddish-tinged yellow
pigment are obtained, which can be directly incorporated, in this
form, into plastics and lacquers. Dyeings which are distinguished
by high fastness properties such as, for example, outstanding
fastness to migration in PVC or fastness to weathering in lacquers,
are obtained.
The tinctorial strength and purity can be improved further if the
pigment is brought to a more finely divided form, whereby the
transparency is also simultaneously increased. Methods which are
particularly suitable for achieving this strongly coloured, pure
and transparent form are, for example, alkaline reprecipitation,
such as is described in British Pat. No. 1,219,041 , and substrate
grinding with hexachloroethane, such as is described in DAS
1,209,852.
If, in this example, the 2.7 g of p-phenylene-diamine are replaced
by equimolar amounts of the diamines listed in column A in Table I,
pigments which display high fastness properties are again obtained.
Column B describes the colour in lacquers. ##SPC14##
EXAMPLES 45 to 73
If in Example 4, instead of the 15.5 g of
3,4,6-trichloro-5-methoxy-o-cyanobenzoic acid methyl ester,
equimolar amounts of the o-cyanobenzoic acid methyl esters listed
in column A of Table II are used and exactly the same procedure is
followed, sparingly soluble dyestuffs are again produced. They are
suitable for pigmenting plastics and lacquers and show, in PVC, the
colour shades described in column B.
Table III shows a number of pigments which were also manufactured
according to the instructions of Example 4, but in which both the
3,4,6-trichloro-5-methoxy-o-cyanobenzoic acid methyl ester and the
-phenylene-diamine were replaced by equimolar amounts of the
o-cyanobenzoic acid esters listed in column A and the diamines
listed in cloumn B. The colour shades in PVC films are described in
column C. ##SPC15##
EXAMPLE 74
Mixed synthesis. If in Example 4, instead of the 15.5 of
3,4,6-trichloro-5-methoxy-o-cyanobenzoic acid methyl ester a
mixture of 7.75 g of this ester and 9.4 g of
3,4,6-trichloro-5-phenoxy-o-cyanobenzoic acid methyl ester is used
and exactly the same procedure is followed, a yellow pigment is
obtained which is suitable for pigmenting plastics and
lacquers.
EXAMPLE 75
If in the preceding example the 9.4 g of
3,4,6-trichloro-5-phenoxy-o-cyanobenzoic acid methyl ester are
replaced by 7.9 g of 3,4,5,6-tetrachloro-o-cyanobenzoic acid methyl
ester, a yellow pigment which displays high fastness properties is
again produced.
EXAMPLE 76
2 g of the pigment manufactured according to EXample 1 are mixed
and ground on a triple-roll mill with 36 g of hydrated alumina, 60
g of linseed oil varanish of medium viscosity and 0.2 g of cobalt
linoleate. The yellow-orange prints produced with this colour paste
are distinguished by outstanding fastness to light.
EXAMPLE 77
0.6 g of the pigment manufactured according to Example 4 is mixed
with 67 g of polyvinyl chloride, 33 g of dioctyl phthalate, 2 g of
dibutyl-tin dilaurate and 2 g of titanium dioxide and the mixture
is milled for 15 minutes on a triple-roll mill. The colour of the
yellow polyvinyl chloride films produced therewith is fast to
migration, heat and light.
EXAMPLE 78
10 g of titanium oxide and 2 g of the pigment manufactured
according to Example 4 and listed under 14 in the table are ground
with 88 g of a mixture of 26.4 g of coconut alkyd resin, 24.0 g of
melamine-formaldehyde resin (50% solids content), 8,8 g of ethylene
glycol monomethyl ether and 28.8 of xylene for 48 hours in a ball
mill.
If this lacquer is sprayed onto an aluminium foil, pre-dried for 30
minutes at room temperature and subsequently stoved for 30 minutes
at 120.degree.C, an orange lacquering which is distinguished by
very good fastness to overlacquering, light and weathering is
obtained.
* * * * *